CN107814992B - A kind of rubber compound of hydrogenated nitrile rubber heat-resistant system and its preparation method - Google Patents

Abstract

The invention discloses a rubber compound of a hydrogenated nitrile rubber heat-resistant system and a preparation method thereof. The raw materials are calculated in parts by mass, high-strength hydrogenated nitrile rubber (ZSC) 85±3 parts, hydrogenated nitrile rubber (HNBR) 15±3 parts, 4,4'-bis(α,α-dimethylbenzyl base) 1.5 ± 0.3 parts of diphenylamine, 2 ± 0.5 parts of dicumyl bis-tert-butyl peroxide, 0-16 parts of aramid pulp, and the mass fraction of aramid pulp is not 0. The rubber compound improves and strengthens the high-temperature mechanical properties of the modified HNBR rubber parts, especially the high-temperature tensile strength of the rubber parts after aging.

Description

A kind of rubber compound of hydrogenated nitrile rubber heat-resistant system and its preparation method

technical field

The invention relates to the technical field of rubber product rubber, in particular to a rubber product rubber of a modified hydrogenated nitrile rubber HNBR heat-resistant system and a preparation method thereof.

Background technique

In recent years, with the continuous increase of my country's crude oil extraction, oil drilling and production projects have also increased. In the process of oil drilling, a large number of rubber products are usually used, such as rubber packers, screw pump stators, sealing rings, etc. These rubber products have a very obvious role in oil drilling.

Packer is an important downhole delamination tool in oil production, and it is widely used in drilling, water injection, delamination oil recovery and gas lift. The quality of its working performance directly affects the production cost and the economic benefits of the enterprise. The packer rubber cylinder is the most important part to ensure the sealing performance of the packer, and the performance of the packer rubber cylinder is of great importance to the working performance of the packer.

The screw pump is a widely used oil production machine at home and abroad. Its structure is simple, it is especially suitable for oil wells with high viscosity and high sand content and has high working efficiency. A rotary pump in which the volume of a space changes and moves to deliver or pressurize a liquid. Its main working parts are rotor and stator. The main failure mode of the screw pump is the failure of the stator.

The sealing ring is an annular cover composed of one or several parts, which is fixed on a ring or washer of the bearing and contacts with another ring or washer or forms a narrow labyrinth gap to prevent the leakage of lubricating oil and the intrusion of foreign objects. The sealing ring has the characteristics of simple structure, easy manufacture, convenient assembly, low cost and reliable use.

In the process of heavy oil production in offshore oilfields, due to environmental conditions, operating space, operating costs and other factors, the application of conventional thermal recovery development methods and process technologies in land oilfields is greatly restricted, and the production difficulty is much higher than onshore Heavy oil field. How to develop these resources efficiently and at low cost is a difficult problem and challenge for offshore heavy oil fields. In order to realize the efficient development of offshore heavy oil fields, offshore heavy oil steam huff and puff oil recovery technology is adopted. Offshore heavy oil steam huff and puff oil recovery technology is a method to achieve high-efficiency development of heavy oil wells by injecting high-temperature and high-pressure steam, hot water and other thermal fluids into the formation, and through mechanisms such as heating to reduce viscosity and steam injection to improve recovery. In the process of oil production, high-temperature fluid is injected into the formation through the tubing, and the temperature of the bottom hole casing, cement sheath and formation rises. Due to the difference in expansion coefficient between the casing and the cement sheath or the formation, it is possible that the casing and the cement sheath will be stretched due to heat. The difference in length leads to the failure of the cemented surface and the hidden danger of gas channeling. At the same time, the high temperature in the wellbore puts forward higher requirements on the high temperature resistance of downhole oil production tools. If the temperature of the oil production tool is too high, it will easily cause the aging of the rubber parts, and the mechanical properties of the aged rubber parts will decrease, resulting in the failure of the rubber parts and affecting the production of the oil field.

Contents of the invention

In order to solve the deficiencies in the prior art, one of the purposes of the present invention is to provide a rubber compound of a hydrogenated nitrile rubber heat-resistant system, which improves and strengthens the high-temperature mechanical properties of modified HNBR rubber parts, especially the aging of rubber parts After high temperature tensile strength.

In order to achieve the above object, the technical solution of the present invention is:

A kind of rubber compound of hydrogenated nitrile rubber heat-resistant system, its raw materials are calculated in parts by mass, 85 ± 3 parts of high-strength hydrogenated nitrile rubber (ZSC), 15 ± 3 parts of hydrogenated nitrile rubber (HNBR), 1.5±0.3 parts of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, 2±0.5 parts of dicumyl peroxide, 0-16 parts of aramid pulp, and The mass fraction of rayon pulp is not zero.

In order to obtain the above-mentioned rubber product compound, the second object of the present invention is to provide a preparation method of the above-mentioned rubber product compound,

(1) Add high-strength hydrogenated nitrile rubber (ZSC) and hydrogenated nitrile rubber (HNBR) to the open mill and mix until the roll is covered; then add 4,4'-bis(α,α-dimethylbenzyl Base) after diphenylamine has finished eating, adopt the triangular bag operation method to carry out refining;

(2) After adding aramid pulp, cutting and cutting, after cooling, add bis-tert-butyl peroxide dicumyl peroxide, after eating, carry out thin-toned triangular bagging, cutting, and park to obtain film ;

(3) The above rubber compound can be obtained by performing one-stage vulcanization and two-stage vulcanization on the film in sequence.

The third object of the present invention is to provide the above-mentioned rubber product compound or the rubber product compound obtained by the above-mentioned preparation method for use in a packer rubber cartridge.

The beneficial effects of the present invention are:

When the test temperature is 150°C, the high-temperature mechanical properties of the modified HNBR vulcanizate after aging have been significantly improved, especially when the amount of aramid pulp is 4 parts, the high-temperature tensile strength of the modified HNBR vulcanizate after aging has been greatly improved. Improvement, the highest tensile strength at 150°C is 16.89MPa, an increase of up to 30%. The high-temperature tensile strength after aging is not the same as the high-temperature mechanical properties solved by the present invention. The prior art only characterizes the high-temperature mechanical properties without aging, but does not characterize the high-temperature properties after aging. The reason is that aromatic Compared with rubber, aramid fiber has outstanding high temperature resistance. Aramid fiber does not melt or decompose at a temperature of up to 460°C; in addition, the modified HNBR blend rubber is not fully vulcanized, and occurs during the aging process. Further cross-linking is mainly manifested in the cross-linking reaction between the nitrile rubber in the aramid pulp and the original blend rubber. The nitrile rubber acts as a bridge to fill the gap and strengthen the "aramid short fiber-pulp- The interaction between the modified HNBR" effectively strengthens the interface between the fiber and the rubber matrix, and the breakage of the aramid short fiber increases instead of being pulled out, so that the high temperature resistance advantage of the aramid fiber can be brought into play, and the modified HNBR is improved. High temperature mechanical properties of vulcanizates. The two-stage vulcanization can complete the reaction of the remaining unreacted cross-linking groups after the one-stage vulcanization, and remove the cross-linking reaction residue generated in the one-stage vulcanization, thereby improving the mechanical properties and compression set at room temperature, and reducing the shrinkage of the product . If the two-stage vulcanization is not carried out, the mechanical properties and compression set at room temperature will be reduced, and the shrinkage rate of the product will be increased. Process parameters: Rubber products are made of 85 parts by mass of high-strength hydrogenated nitrile rubber (ZSC) and 15 parts by mass of hydrogenated nitrile rubber (HNBR). At these parts by mass, the high-temperature mechanical properties of the vulcanized rubber are the best. good.

Description of drawings

The accompanying drawings constituting a part of the present application are used to provide further understanding of the present application, and the schematic embodiments and descriptions of the present application are used to explain the present application, and do not constitute improper limitations to the present application.

Fig. 1 is a histogram of the tensile strength of the samples prepared in each embodiment.

Detailed ways

It should be pointed out that the following detailed description is exemplary and is intended to provide further explanation to the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It should be noted that the terminology used here is only for describing specific implementations, and is not intended to limit the exemplary implementations according to the present application. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural, and it should also be understood that when the terms "comprising" and/or "comprising" are used in this specification, they mean There are features, steps, operations, means, components and/or combinations thereof.

As introduced in the background technology, there is a deficiency in the prior art that the mechanical properties of rubber parts after aging reduce the rubber parts to fail. In order to solve the above technical problems, this application proposes a rubber of hydrogenated nitrile rubber heat-resistant system Product glue and preparation method.

A typical implementation of the present application provides a rubber product compound of a hydrogenated nitrile rubber heat-resistant system. Nitrile rubber (HNBR) 15±3 parts, 4,4'-bis(α,α-dimethylbenzyl) diphenylamine 1.5±0.3 parts, bis-tert-butyl peroxide dicumyl 2±0.5 parts, 0-16 parts of aramid pulp, and the mass fraction of aramid pulp is not 0.

Preferably, the mass fraction of the aramid pulp is 4. When the amount of aramid pulp is 4 parts, the high temperature tensile strength of the vulcanized rubber after aging is greatly improved, and the highest tensile strength at 150°C is 16.89MPa, which is as high as 30%.

Preferably, the high-strength hydrogenated nitrile rubber contains 50-55% (by mass) of zinc methacrylate.

Another embodiment of the present application provides a method for preparing the above rubber compound,

(1) Add high-strength hydrogenated nitrile rubber (ZSC) and hydrogenated nitrile rubber (HNBR) to the open mill and mix until the roll is covered; then add 4,4'-bis(α,α-dimethylbenzyl Base) after diphenylamine has finished eating, adopt the triangular bag operation method to carry out refining;

(2) After adding aramid pulp, cutting and cutting, after cooling, add bis-tert-butyl peroxide dicumyl peroxide, after eating, carry out thin-toned triangular bagging, cutting, and park to obtain film ;

(3) The above rubber compound can be obtained by performing one-stage vulcanization and two-stage vulcanization on the film in sequence.

Preferably, the kneading conditions in step (1) are as follows: the temperature of the front roll is 30-50°C, and the temperature of the rear roll is 45-55°C. Further preferably, the distance between the front roller and the rear roller is 3±0.5mm.

Preferably, step (1) uses the triangular bag operation method to carry out the refining times for 4 to 6 times.

Preferably, the number of cutting knives in step (2) is 3 to 4 times for each of the cutting knives on both sides.

Preferably, the number of times of the Botongda triangular bag described in step (2) is 6 to 8 times.

Preferably, the parking time described in step (2) is more than 8h. In order to improve work efficiency, it is further preferred that the parking time in step (2) is 8-24 hours.

Preferably, the method for determining the first-stage vulcanization conditions described in step (3) is: use a rotorless vulcanizer to detect the scorch time (t ₁₀ ) and positive vulcanization time (t ₉₀ ) of the mixed rubber, and then vulcanize the sample with a flat vulcanizer , Determine the appropriate curing temperature according to the positive curing time _t90 .

Preferably, the one-stage vulcanization conditions in step (3) are as follows: temperature is 170±5° C., pressure is 15±0.5 MPa, and time is 10±1 min.

Preferably, the conditions for the second-stage vulcanization described in step (3) are as follows: heat the rubber material after the first-stage vulcanization to 70±2°C and keep it warm for 0.4-0.6h; then raise the temperature to 100±5°C and keep it warm for 0.4-0.6h ;Continue to heat up to 130±5°C, keep warm for 0.4~0.6h; finally raise the temperature to 150±5°C, keep warm for 3~4h.

The third embodiment of the present application provides the application of the above-mentioned rubber product compound or the rubber product compound obtained by the above-mentioned preparation method in a packer rubber cartridge.

In order to enable those skilled in the art to understand the technical solution of the present application more clearly, the technical solution of the present application will be described in detail below in conjunction with specific embodiments.

Example 1

(1) A mixture of modified HNBR raw rubber (85 parts of high-strength hydrogenated nitrile rubber (ZSC) and 15 parts of hydrogenated nitrile rubber (HNBR), wherein the high-strength hydrogenated nitrile rubber (ZSC) contains 55 % (mass) of zinc methacrylate) is added to the open mill, the temperature of the front roll is 40°C, the temperature of the back roll is 50°C, and the roll distance is 3mm. Mixing is carried out until the mixture wraps the front roll and has The rest of the mixture exists between the front and rear rollers, add 1.5 parts of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (N445), and after the feeding is completed, the rollers of the two-roller mill The distance is adjusted to 1mm, and then the triangular bag operation method is used for turning, repeating 4 times.

(2) Add 0 parts of aramid pulp (AP), after eating the material, cut the left and right knife three times, remove the slice, add 2 parts of bis-tert-butyl dicumyl peroxide (BIBP) after cooling, and wait to eat After the material is finished, make a triangular bag six times, unload the film, and park to obtain the film; before the rubber material is vulcanized, it needs to be parked for 12 hours and re-milled for use.

(3) The film is placed on a flat vulcanizer, vulcanized for 10 minutes at a temperature of 170°C and a pressure of 15 MPa, and after the film is vulcanized, it is allowed to stand at room temperature for 12 hours until the second-stage vulcanization.

(4) Put the samples neatly into the oven, raise from normal temperature to 70°C and maintain for 0.5h; then rise to 100°C and maintain for 0.5h; then rise to 130°C and maintain for 0.5h; finally rise to 150°C , Take it out after maintaining for 3h. After the second-stage vulcanization, the sheet was parked at room temperature for an appropriate period of time, and then punched with a cutting knife for high-temperature mechanical performance testing.

Embodiment 2: The difference between this experimental example and Experimental Example 1 is that the number of aramid pulp (AP) in step (2) is 4 parts, and other steps and parameters are the same as in Example 1.

Embodiment 3: The difference between this experimental example and experimental example 1 is that the number of aramid pulp (AP) in step (2) is 8 parts, and other steps and parameters are the same as in embodiment 1.

Embodiment 4: The difference between this experimental example and Experimental Example 1 is that the number of aramid pulp (AP) in step (2) is 12, and other steps and parameters are the same as in Example 1.

Embodiment 5: The difference between this experimental example and experimental example 1 is that the number of aramid pulp (AP) in step (2) is 16 parts, and other steps and parameters are the same as in embodiment 1.

When the amount of aramid pulp is 4 parts, the performance of modified HNBR:

1. Mechanical properties

2. High temperature mechanical properties

3. Heat air aging resistance and compression set performance

High temperature tensile strength after aging Tensile Strength Retention tear strength retention Compression set/C% 16.89 131.77 89.40 36

When the amount of aramid pulp is 8 parts, the performance of modified HNBR:

1. Mechanical properties

2. High temperature mechanical properties

3. Performance of vulcanized rubber after aging and compression set performance

High temperature tensile strength after aging Tensile Strength Retention tear strength retention Compression set/C% 13.34 99.92 83.12 41

The tensile strengths of the samples prepared in Examples 1-5 are shown in FIG. 1 . It can be clearly seen from Figure 1 that when the amount of aramid pulp is 4 parts, the high-temperature tensile strength of the modified HNBR vulcanizate after aging is greatly improved, and the highest tensile strength at 150°C is 16.89MPa, an increase of up to 30%. .

The above descriptions are only preferred embodiments of the present application, and are not intended to limit the present application. For those skilled in the art, there may be various modifications and changes in the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included within the protection scope of this application.

Claims (5)

1. a kind of rubber product sizing material of the heat-resisting system of hydrogenated nitrile-butadiene rubber, characterized in that raw material is calculated as with mass fraction, high-strength 85 ± 3 parts of hydrogenated nitrile-butadiene rubber of degree, 15 ± 3 parts of hydrogenated nitrile-butadiene rubber, bis- (bis (alpha, alpha-dimethylbenzyl) base) diphenylamines 1.5 of 4,4'- ± 0.3 part, 2 ± 0.5 parts of dual-tert-butyl cumyl peroxide, 0~16 part of Fanglun slurry cake, and the mass fraction of Fanglun slurry cake is not 0；

The preparation method comprises the following steps:

(1) high-intensitive hydrogenated nitrile-butadiene rubber and hydrogenated nitrile-butadiene rubber are added to open mill, are kneaded to packet roller；Then 4 are added, After bis- (alpha, alpha-dimethylbenzyl) the diphenylamines material feedings of 4'-, turned refining using triangle bag maneuver；

(2) cutter, bottom sheet are carried out after Fanglun slurry cake material feeding is added, and dual-tert-butyl cumyl peroxide is added after cooling, Carried out after material feeding it is thin it is logical beat triangle bag, bottom sheet parks acquisition film；

(3) film is successively carried out to one step cure and post vulcanization can be obtained above-mentioned rubber product sizing material；

Wherein, the condition of step (1) described mixing are as follows: preceding roll temperature is 30~50 DEG C, and rear roll temperature is 45~55 DEG C；Using three The number that angle package operation method turns refining is 4~6 times；

Cutter number described in step (2) is two sides cutter each 3~4 times；The thin logical number for beating triangle bag is 6~8 times； The storage period is 8h or more；

One step cure condition described in step (3) are as follows: temperature be 170 ± 5 DEG C, pressure be 15 ± 0.5MPa, the time be 10 ± 1min；The condition of the post vulcanization are as follows: the sizing material after one step cure is warming up to 70 ± 2 DEG C, keeps the temperature 0.4~0.6h；Again 100 ± 5 DEG C are warming up to, 0.4~0.6h is kept the temperature；130 ± 5 DEG C are continuously heating to, 0.4~0.6h is kept the temperature；Finally it is warming up to 150 ± 5 DEG C, keep the temperature 3~4h.

2. the rubber product sizing material of the heat-resisting system of hydrogenated nitrile-butadiene rubber as described in claim 1, characterized in that Fanglun slurry cake Mass fraction is 4.

3. the rubber product sizing material of the heat-resisting system of hydrogenated nitrile-butadiene rubber as described in claim 1, characterized in that the high intensity The methacrylic acid for being 50~55% containing mass fraction in hydrogenated nitrile-butadiene rubber.

4. the rubber product sizing material of the heat-resisting system of hydrogenated nitrile-butadiene rubber as described in claim 1, characterized in that preparation method step Suddenly in (1), the roll spacing of preliminary roller and back roller is 3 ± 0.5mm.

5. a kind of rubber product sizing material of any heat-resisting system of hydrogenated nitrile-butadiene rubber of Claims 1 to 4 is in packer rubber It is applied in cylinder.